This invention relates to catalysts useful in the oxidation of hydrocarbons. for example butadiene. The catalysts comprise vanadium oxides incorporated in a matrix comprising oxides and oxyhydroxides of silicon, titanium, tantalum and/or niobium derived using sol gel chemistry.
This invention relates to a catalyst comprising vanadium oxides incorporated in a matrix comprising oxides and oxyhydroxides of silicon, titanium. tantalum and/or niobium derived using sol gel chemistry, optionally in the presence of an organic directing agent. This invention also relates to a process for the preparion of furan and maleic anhydride, more specifically, to a method for preparing furan and maleic anhydride by a vapor-phase catalytic oxidation reaction from 1,3 butadiene.
Furan is used as a chemical building block for the production of other industrial chemicals such as tetrahydrofuran, pyrrole and thiophene. Maleic anhydride can be used to manufacture tetrahydrofuran, polyester resins, fumaric and tartaric acids, pesticides, preservatives and other industrial products.
E. I. Ko, in the Handbook of Heterogeneous Catalysis, ed. by G. Ertl et al, Vol. 1. 2.1.4 (1997) reviews generally the use of sol-gel processes for the preparation of catalytic materials. There is no disclosure of or suggestion of vanadium oxides, vanadium phosphorus oxides, or vanadium antimony oxides dispersed in and distributed throughout high surface area oxides of silicon and/or titanium as being useful catalysts for the oxidation of butadiene.
Japanese Patent Application SHO 46-22009 discloses the preparation of catalysts comprising oxides of molybdenum, bismuth and vanadium in a silica matrix and their utility in the oxidation of butadiene.
U.S. Pat. No. 4,622,310 discloses inorganic phosphate aerogels. The utility disclosed is as porous inert carrier materials (supports) in polymerization and copolymerization processes. Use of the inorganic phosphates as supports in hydrocarbon oxidation processes wherein the catalyst species is V2O5, MoO3, Ag. Cu, PCI3 and BiO23 (sic. Bi2O3 is meant) are described. There is no disclosure nor suggestion of incorporating the catalytic material within the inorganic phosphate gel matrix.
U.S. Pat. No. 5,264,203 describes the preparation of large pore crystalline materials, for example silicoaluminophosphates, optionally comprising a metal, by use of an organic directing agent.
This invention provides compositions comprising catalytic species selected from the group consisting of vanadium oxides, vanadium phosphorous oxides and vanadium antimony oxides incorporated in a matrix material selected from the group of oxides and oxyhydroxides of silicon, titanium, tantalum and niobium, which compositions are prepared by sol gel chemistry, optionally in the presence of an organic directing agent.
This invention further provides an improved process for the oxidation of butadiene to furan and maleic anhydride, the improvement comprising the use of a composition comprising catalytic species selected from the group consisting of vanadium oxides, vanadium phosphorous oxides and vanadium antimony oxides incorporated in a matrix material selected from the group of oxides and oxyhydroxides of silicon, titanium, tantalum and niobium, which compositions are prepared by sol gel chemistry, optionally in the presence of an organic directing agent.
Catalysts that are highly reactive for the oxidation of butadiene were synthesized by incorporating catalyst species into matrices containing silicon, titanium, tantalum and niobium oxides and oxyhydroxides to generate high surface area catalysts. Specific catalytic species employed include vanadium oxides, vanadium phosphorus oxides, and vanadium antimony oxides. Bar matrix is meant a skeletal framework of oxides and oxyhydroxides which can be derived from the hydrolysis of alkoxides and other reagents.
The catalysts of the present invention may be prepared by various methods. A non-aqueous solution containing the catalyst species and matrix precursors (generally, but not necessarily, alkoxides) is added to solution containing water, acid or base, alcohol and, optionally, an organic directing agent to form a catalyst precursor gel or gelatinous material and subsequently drying the gel. Alternatively, a solution containing water, acid or base and alcohol is added to a nonaqueous solution containing catalyst species, matrix precursors, and, optionally, an organic directing agent. In general, the optional organic directing agent can be in the aqueous or non-aqueous solutions. The catalytically active species can be in the aqueous or non-aqueous solutions. The order can be (i) aqueous solutions added to non-aqueous solutions, or (ii) non-aqueous solutions added to aqueous solutions.
The inorganic metal alkoxides used in this invention, i.e. the alkoxides of silicon, titanium, tantalum and niobium may include any alkoxide which contains from 1 to 20 carbon atoms and preferably 1 to 5 carbon atoms in the alkoxide group, which are preferably soluble in the liquid reaction medium. In this invention, preferably, C1-C4 systems, ethoxides, isopropoxides or n-butoxides are used.
One of the criteria for the starting material are inorganic alkoxides or metal salts which will dissolve in the specified medium or solvent. Commercially available alkoxides can be used. However, inorganic alkoxides can be prepared by other routes. Some examples include direct reaction of zero valent metals with alcohols in the presence of a catalyst. Many alkoxides can be formed by reaction of metal halides with alcohols. Alkoxy derivatives can be synthesized by the reaction of the alkoxide with alcohol in a liqand interchange reaction. Direct reactions of dialkylamideg with acohol also form alkoxide derivatives.
The catalytic species, i.e., the vanadium oxides, vanadium phosphorous oxides and vanadium antimony oxides are derived from soluble alkoxides or salts. Preferred species include NH4VO3, vanadium trisisopropoxide, and antimony (III) n-butoxide (Sb (OC4H9)3.
The organic direct agent, if present, is selected from the group consisting aliphatic amines, aromatic amines, cyclic aliphatic amines, polycyclic aliphatic amines and an amonium or phosphonium ion. A preferred organic directing agent is dodecylamine.
After combining the solutions employed, the alkoxides will react and polymerize to form a gel. As polymerization and crosslinking proceeds viscosity increases and the material can eventually set to a rigid xe2x80x9cgelxe2x80x9d. The xe2x80x9cgelxe2x80x9d consists of a crosslinked network of the desired material which incorporates the original solvent within its open porous structure. The xe2x80x9cgelxe2x80x9d may then be dried, typically by either simple heating in a flow of dry air to produce an aerogel or the entrapped solvent may be removed by displacement with a supercritical fluid such as liquid CO2 to produce an aerogel, as described below. Final calcination of these dried materials to elevated temperatures ( greater than 200xc2x0 C.) results in products which typically have very porous structures and concomitantly high surface areas.
Depending on the alkoxide system and the water/alkoxide ratios used, a discernible gel point can be reached immediately or hours later. The molar ratio of the total water added (including water present in aqueous solutions), can vary according to the specific inorganic alkoxide being reacted. Generally, a molar ratio of water to alkoxide within the broad range of 3 to 150 is within the scope of this invention. It is understood that the order of addition of the various solutions can be reversed.
The addition of acidic or basic reagents to the gellation reaction can have an effect on the kinetics of the hydrolysis and condensation reactions, and the microstructure of the oxide/hydroxide matrices derived from the alkoxide precursor which entraps or incorporates the soluble metal reagents. Generally, a pH range of 1-12 can be used, with a pH range of 1-6 preferred for these experiments.
After reaction, the catalytic species is uniformly incorporated into the gel network. Further processing to produce the final catalytic material may include a combination of calcination cycles in various media.
The solvent in the gels can be removed in several different ways: conventional drying, freeze and vacuum drying, spray drying, or the solvent can be exchanged under supercritical conditions. Removal by vacuum drying results in the formation of a xerogel. An aerogel of the material can typically be formed by charging in a pressurized system such as an autoclave. The solvent laden gel which is formed in the practice of the invention is placed in an autoclave where it can be contacted with a fluid above its critical temperature and pressure by allowing supercritical fluid to flow the material solid and liquid until the solvent is no longer being extracted by the supercritical fluid. In performing this extraction to produce the aerogel material, various fluids can be utilized at their critical temperature and pressure. For instance, fluorochlorocarbons typified by Freon brand fluorochloromethanes and ethanes, ammonia and carbon dioxide are all suitable for this process. Typically, the extraction fluids are fluids which are gases at atmospheric conditions, so that pore collapse due to the capillary forces at the liquid/solid interface are avoided during drying. The resulting material should, in most cases, possess a higher surface area than the non-supercritically dried materials.
Prior to calcination, the compositions of the present invention may show a X-ray diffraction pattern containing low angle peaks indicating the quasi-regular arrangement of mesopores which containing the organic directing agent. This is evident for catalyst precursors described in Example 2 and Example 3 before calcination, which possess low angle lines at 2.38 degrees two theta, 2.70, 4.990, 7.175 two theta (Example 2) and 2.41 degrees, 262 degrees, 5.11 degrees, 7.20 degrees, and 7.74 degrees two theta (Example 3) indicating approximately 37 Angstrom pores. The size and shape of the organic directing agent filled pores can depend on the geometry of the organic directing agent and their agglomerates or micelles. The organic directing agent may act as a template for nucleation and growth of the organic directing agent filled mesoporougs matrix, which also contains the inorganic and active component. By mesoporous, we mean 15 angstroms to 200 angstroms in diameter. Following high temperature calcination in air, the organic directing agent is removed and crystalline order is lost. The directing agent may also be removed by chemical oxidation or other methods. Powder X-ray data was obtained using a Scintag Powder X-ray Diffractometer. with 0.01 degrees 2xcex8 steps, 1.199 seconds per step, Kxcex11 Cu radiation.
It is believed that the organic directing agent, optionally present in the present invention, serves as a template for the inorganic oxide so that a large unit cell is observed in powder X-ray diffraction data before calcination of the inorganic oxide. In the case of the titanium and niobium oxides, after calcination, i.e., after the organic directing agent is removed by air oxidation, long range order is lost and the material no longer exhibits the low angle X-ray diffraction peaks indicative of the mesoporous (approximately 37 A) unit cell. In the case of the silica containing catalysts, the low angle X-ray diffraction peaks are still apparent, indicating quasi-crystalline order is maintained for the large unit cell. For the catalysts of the present invention, calcination is carried out in the temperature range 300-800xc2x0 C., for a time sufficient to remove the organic directing agent, usually in the time range from 30 minutes to  greater than 48 hours.
As an example of the improved catalytic activity obtained, the apparent first order rate constant for butadiene oxidation using VPO (vanadyl pyrophosphate) catalyst is 0.4 secxe2x88x921 (at 300xc2x0 C.), compared with 3.8 secxe2x88x921 for the sol-gel derived vanadium/silicon oxide catalyst of the present invention. The vanadium/titania and vanadium/antimony/titanium oxide systems show further activity improvements over previously known catalysts.